Hydrocracking catalyst and process using a magnesium aluminosilicate clay

ABSTRACT

This invention is directed to hydrocracking catalysts and hydrocracking processes employing a magnesium aluminosilicate clay and a zeolite. The magnesium aluminosilicate clay has a characteristic  29 Si NMR spectrum. The magnesium aluminosilicate clay is the product of a series of specific reaction steps. The resulting magnesium aluminosilicate clay combines high surface area and activity for use in hydrocracking catalysts and processes.

This application is a Continuation of U.S. application Ser. No.13/344,040 filed Jan. 8, 2013, now U.S. Pat. No. 8,603,932, which is aDivisional of U.S. application Ser. No. 12/245,548 filed Oct. 3, 2008,now U.S. Pat. No. 8,518,239.

FIELD OF THE INVENTION

This invention is directed to hydrocracking catalysts and hydrocrackingprocesses employing a magnesium aluminosilicate clay.

BACKGROUND OF THE INVENTION

Hydrocracking catalysts can comprise various components. Generally,hydrocracking catalysts comprise at least one acidic component thathelps convert high molecule weight hydrocarbons to lower molecularweight hydrocarbons. One type of acidic component used in hydrocrackingcatalysts is an acidic clay such as a magnesium aluminosilicate clay.Magnesium aluminosilicate clays can be described as a type of layeredmaterial comprising alternating sheets of octahedrally co-ordinatedmagnesium atoms and tetrahedrally co-ordinated silicon and/or aluminumatoms. Magnesium aluminosilicate clays have a negative layer chargewhich can be balanced by cations. Among other characteristics, the typeof charge balancing cations imparts catalytic activity to the magnesiumaluminosilicate clays. The literature contains examples of magnesiumaluminosilicate clays used as hydrocracking catalysts or as componentsof hydrocracking catalysts.

While synthesis of clays can be difficult, particularly on a largescale, clays have received attention for use in catalytic processes suchas (hydro)cracking. For example,

U.S. Pat. No. 3,844,978 discloses a layer-type, dioctahedral, clay-likemineral useful in catalytic cracking processes. The clay-like mineral isa magnesium aluminosilicate that can be used as a catalyst or as acomponent in a catalyst composition.

U.S. Pat. No. 3,844,979 discloses a layer-type trioctahedral, clay-likemineral that is a magnesium aluminosilicate, a catalyst compositioncomprising said magnesium aluminosilicate, and hydroprocesses using saidmagnesium aluminosilicate.

U.S. Pat. No. 3,887,454 discloses hydroconversion processes using alayer-type, dioctahedral, clay-like mineral that is a magnesiumaluminosilicate. Catalyst compositions and hydroprocessing reactionsusing catalyst compositions comprising magnesium aluminosilicates andhydrogenation components such as Group VIII metals are also disclosed.

U.S. Pat. No. 6,187,710 and U.S. Pat. No. 6,565,643 disclose syntheticswelling clay minerals, methods of making swelling clay minerals, andthe use of said swelling clay minerals as hydrocarbon reactioncatalysts. U.S. Pat. No. 6,334,947 discloses catalysts compositionscomprising a swelling clay and the use of said catalyst compositions inhydroprocessing reactions. Magnesium aluminosilicates are examples ofswelling clays disclosed in U.S. Pat. No. 6,187,710, U.S. Pat. No.6,565,643, and U.S. Pat. No. 6,334,947.

There exists a need for magnesium aluminosilicate clays with improvedcharacteristics that can be used as catalysts or components of catalystcompositions in hydrocracking.

SUMMARY OF THE INVENTION

This application discloses hydrocracking catalysts comprising amagnesium aluminosilicate clay wherein the magnesium aluminosilicateclay is synthesized according to a process comprising the followingsteps:

-   -   a) combining (1) a silicon component, (2) an aluminum component,        and (3) a magnesium component, under aqueous conditions at a        first reaction temperature and at ambient pressure, to form a        first reaction mixture, wherein the pH of said first reaction        mixture is acidic;    -   b) adding an alkali base to the first reaction mixture to form a        second reaction mixture wherein the pH of the second reaction        mixture is greater than the pH of the first reaction mixture;    -   c) reacting the second reaction mixture at a second reaction        temperature and for a time sufficient to form a product        comprising a magnesium aluminosilicate clay.

Also included within the present invention are hydrocracking catalysts,comprising the magnesium aluminosilicate clay as set forth above,wherein said hydrocracking catalysts further comprise one or morecatalytically active metals, zeolites, inorganic oxides, or combinationsthereof. Particularly useful catalytically active metals are Group VIBand/or Group VIII metals, particularly platinum, palladium, cobalt,nickel, molybdenum, and tungsten.

This application also discloses hydrocracking catalyst compositionscomprising a magnesium aluminosilicate clay wherein said magnesiumaluminosilicate clay has a silicon to aluminum elemental mole ratiogreater than 3 and wherein the ²⁹Si NMR of the magnesium aluminosilicateclay comprises peaks as given in Table 1:

TABLE 1 Chemical Peaks shift (ppm)¹ P1 −79 P2 −82 P3 −85 P4 −88 P5 −93¹+/−3 ppm

In an embodiment, the magnesium aluminosilicate clay is mesoporous.

Hydrocracking processes employing the catalysts described above alsoform part of this invention.

Other objects and advantages will become apparent from the detaileddescription and the appended claims.

DETAILED DESCRIPTION OF THE INVENTION

The catalysts of the invention comprise a magnesium aluminosilicateclay. The magnesium aluminosilicate clay is prepared by the followingsteps:

-   -   a) combining (1) a silicon component (2) an aluminum component,        and (3) a magnesium component, under aqueous conditions at a        first reaction temperature and at ambient pressure, to form a        first reaction mixture, wherein the pH of said first reaction        mixture is acidic;    -   b) adding an alkali base to form a second reaction mixture        wherein the pH of the second reaction mixture is greater than        the pH of the first reaction mixture;    -   c) reacting the second reaction mixture at a second reaction        temperature and for a time sufficient to form the magnesium        aluminosilicate clay.

The magnesium aluminosilicate clay can then be converted to a protonatedform by exchanging the alkali cations in an ion exchange reaction.Generally, the alkali cations are exchanged for ammonium cations. Theresulting ammonium substituted magnesium aluminosilicate clay is thendeammoniated by calcination resulting in the protonated form of themagnesium aluminosilicate clay. Calcination of the magnesiumaluminosilicate clay can occur prior to, during, or after formation ofthe hydrocracking catalyst. The magnesium aluminosilicate claysynthesized by the above described process can be composited with anumber of other components to form the catalyst of the invention.Examples of other components include, but are not limited to, zeolites,inorganic oxides, active metals, molecular sieves, and other clays.Catalysts prepared as outlined above can be used for a wide variety ofhydroprocessing reactions. The catalysts are of particular use inhydrocracking processes. The invention is further directed tohydrocracking processes employing the catalysts.

Definitions

While the invention is susceptible to various modifications andalternative forms, specific embodiments thereof are herein described indetail. It should be understood, however, that the description herein ofspecific embodiments is not intended to limit the invention to theparticular forms disclosed, but on the contrary, the intention is tocover all modifications, equivalents, and alternatives falling withinthe spirit and scope of the invention as defined by the appended claims.

The following terms will be used throughout the specification and willhave the following meanings unless otherwise indicated.

As used herein “hydrothermal” refers to reactions performed in thepresence of water or steam at temperatures above 100° C. and atpressures above atmospheric pressures (i.e. above about 1.2 bar).

As used herein “hydrocarbon” refers to any compound which compriseshydrogen and carbon, and “hydrocarbon feedstock” refers to any chargestock which contains greater than about 90 weight percent carbon andhydrogen.

As used herein “Group VIB” or “Group VIB metal” refers to one or moremetals, or compounds thereof, selected from Group VIB of the CASPeriodic Table.

As used herein “Group VIII” or “Group VIII metal” refers to one or moremetals, or compounds thereof, selected from Group VIII of the CASPeriodic Table.

As used herein “cracking” refers to the breaking of larger carboncontaining molecules into smaller ones. Cracking can refer tohydrocracking wherein the cracking takes place in the presence of anelevated partial pressure of hydrogen gas. Cracking also refers tocatalytic cracking wherein the cracking takes place in the presence ofacid catalysts.

As used herein “aqueous mixture” refers to a combination of one or morecomponents in the presence of water. The components can be soluble,somewhat soluble, or insoluble. The aqueous mixture can be homogeneousor heterogeneous.

The term “mesoporous” refers to an average pore size of about 2 to 50nm.

The term “ambient pressure” refers to pressures in the range of about0.9 bar to about 1.2 bar.

The BET surface area is determined by adsorption of nitrogen at 77K andmesopore surface area by the BJH method (described in E. P. Barrett, L.C. Joyner and P. H. Halenda, J. Amer. Chem. Soc., 73, 1951, 373.). Themicropore volume is determined by the DR equation (as described inDubinin, M. M. Zaverina, E. D. and Raduskevich, L. V. Zh. Fiz. Khimii,1351-1362, 1947). The total pore volume is determined from the nitrogenadsorption data, the mesopore volume is determined by the differencebetween total pore volume and the micropore volume.

²⁹Si NMR spectra can be collected at a spinning speed of 8 kHz with atleast 500 scans and a relaxation time of 100 seconds between scans.

The synthesis process for making the magnesium aluminosilicate clayemployed in the invention comprises forming an aqueous mixture of asilicon component, an aluminum component, and a magnesium componentunder acidic conditions to form a first reaction mixture. As used herein“component” refers to any material, salt, and/or compound comprising agiven element which can act as a source of said element. For example“silicon component” can refer to silicon in the elemental form, siliconcontaining compounds, and/or silicon salts which can be used as a sourceof silicon. Examples of silicon components include, but are not limitedto, sodium silicate, potassium silicate, silica gels, silica sols, andcombinations thereof. In one embodiment, the silicon component is sodiumsilicate. Examples of aluminum components include, but are not limitedto, sodium aluminate, potassium aluminate, aluminum sulfate, aluminumnitrate, and combinations thereof. In one embodiment of the invention,the aluminum source is aluminum nitrate. Examples of magnesiumcomponents include, but are not limited to, magnesium metal, magnesiumhydroxide, magnesium halides, magnesium sulfate, and magnesium nitrate.In one embodiment of the invention the magnesium component is magnesiumnitrate.

In the first reaction mixture, the ratio of silicon to aluminum tomagnesium, can be expressed in terms of elemental mole ratios as:

-   -   aSi:bAl:cMg        wherein “a” has a value from 6 to 8, “b” has a value from 0.001        to 7.9, and “c” has a value of from 0.1 to 6, wherein        b=(6−c)+(8−a), and wherein a:b is at least 3.

The silicon, aluminum, and magnesium components are combined, underaqueous conditions, to form a first reaction mixture under acidicconditions wherein the first reaction mixture has a pH of between about0 to about 5. The pH of the first reaction mixture can be adjusted bythe addition of an acid in order to achieve a pH of between about 0 toabout 5. Examples of acids include, but are not limited to, mineralacids such as sulfuric acid, hydrochloric acid, and nitric acid. Organicacids such as acetic acid, citric acid, formic acid, and oxalic acid canalso be used.

The first reaction mixture is generally formed under ambient pressureand temperature conditions. Pressures ranges for the reaction arebetween about 0.9 bar and 1.2 bar, preferably between about 1.0 bar andabout 1.1 bar. The temperature for the formation of the first reactionmixture is not critical. Generally, the temperature is between about 0°C. and 100° C. and preferably at least 50° C.

After addition of the silicon, aluminum, and magnesium components andadjustment of the pH to between about 0 to about 5 to form the firstreaction mixture, an alkali base is added to form a second reactionmixture. Examples of alkali base include, but are not limited to, sodiumhydroxide and potassium hydroxide. Sufficient alkali base is added tothe first reaction mixture so as to ensure that the pH of the resultingsecond reaction mixture is at least 7.5.

The second reaction mixture is then reacted for sufficient time and atsufficient temperature to form the magnesium aluminosilicate clay usedin the catalysts and processes of the invention. In embodiments, thetime is at least one second, preferably at least 15 minutes, and mostpreferably at least 30 minutes. In some embodiments, precipitation ofthe magnesium aluminosilicate clay can be instantaneous. The temperatureof the second reaction mixture can range from about 0° C. to about 100°C. In an embodiment, the temperature of the second reaction mixture isat least 50° C. Generally, higher temperatures result is shorter timesto form the magnesium aluminosilicate clay. The second reaction mixturestep can be done at ambient pressure, although higher or lower pressuresare not excluded. In the synthesis process described, the magnesiumaluminosilicate clay is formed in the second reaction mixture step. Insome embodiments, the magnesium aluminosilicate clay quantitativelyprecipitates from the second reaction mixture. The second reactionmixture, upon precipitation of the magnesium aluminosilicate claycomprises the solid magnesium aluminosilicate clay and a supernatant. By“supernatant” it is meant the aqueous portion of the reaction mixturethat is in liquid form, essentially free of solid or particulatematerial. The magnesium aluminosilicate clay can be collected by, forexample, filtration, evaporation of the supernatant, or centrifugation.The addition of an alkali base during the second step of the synthesisprocess will incorporate alkali cations into the magnesiumaluminosilicate clay.

The magnesium aluminosilicate clay can then be washed, and/or dried,and/or ion exchanged, and/or calcined. In embodiments, the magnesiumaluminosilicate clay is subjected to an ion exchange reaction with anammonium salt solution, wherein at least a portion of the alkali in theproduct is exchanged for ammonium cations. The magnesium aluminosilicateclay need not be isolated from the second reaction mixture before ionexchange. For example, an ammonium salt in solid or solution form can bedirectly added to the second reaction mixture after the precipitation ofthe magnesium aluminosilicate clay. Examples of ammonium salts include,but are not limited to, ammonium nitrate, ammonium bicarbonate, andammonium chloride. Generally, the ammonium cations will have the formula[NH_(x)R_(y)]⁺, where R is any alkyl or other organic radical group,x=1-4, y=0-4, and x+y=4. In a preferred embodiment, the ammonium cationsare NH₄ ⁺ cations. After ion exchange the magnesium aluminosilicateproduct can then be separated from the supernatant by filtration,centrifugation, or any other methods known in the art. The product canthen be dried and/or calcined.

The supernatant from the ion exchange step can be collected for use inother applications. For example, if nitric acid was used duringsynthesis and the ion exchange reaction used ammonium cations, theeffluent will be rich in ammonium nitrate. After isolation of themagnesium aluminosilicate clay, the ammonium nitrate rich supernatantcan be used as a fertilizer or as a component in a fertilizer. Becausethe precipitation of the magnesium aluminosilicate product can beessentially quantitative, the supernatant can have essentially nomagnesium, silicon, or aluminum present. The presence of excess amountsof silicon and/or aluminum and/or magnesium would render the supernatantless useful as a fertilizer or fertilizer component. By using thesupernatant as well as the magnesium aluminosilicate clay product, aneconomic benefit can be realized in that there is little waste ofreagents or costly recycling of magnesium, silicon, and/or aluminumcontaining supernatent.

Before use as a catalyst or as a component in a catalyst, the magnesiumaluminosilicate clay can be calcined. The magnesium aluminosilicate claycan be combined with other components before or after calcination.Calcination is generally performed at temperatures between about 450° C.to about 900° C. for a time ranging from about 1 hour to about 12 hoursunder an inert atmosphere. Calcination reaction times and temperaturesare not critical. For example, if the magnesium aluminosilicate claycomprises ammonium cations, the calcination is generally performed atsufficient temperature and for sufficient time so as to deammoniate orremove other nitrogen containing compounds from the product, leavingprotons as the charge compensating ions in the product. By deammoniateit is meant that ammonia is driven off, leaving protons as the chargecompensating ions in the product. The calcination step is necessary toform a catalytically active material.

The product of the above described process is a magnesiumaluminosilicate clay. The ratio of silicon to aluminum in the magnesiumaluminosilicate clay is at least 3. The ratio of silicon to aluminum tomagnesium of the magnesium aluminosilicate clay can be expressed interms of elemental mole ratios:

-   -   dSi:eAl:fMg        wherein “d” has a value from 6 to 8, “e” has a value from 0.001        to 7.9, and “f” has a value of from 0.1 to 6, wherein        e=(6−f)+(8−d), and wherein d:e is at least 3.

The magnesium aluminosilicate clay employed in the catalyst and processof the invention is a layered material composed of elemental clayplatelets. The size of the clay platelets of the magnesiumaluminosilicate clay is dependent on the reacting temperature and thereacting time of the second reaction mixture. Generally, the higher thetemperature and the longer the time, the larger the clay platelets willbe. Depending of the desired size of the clay platelets in the product,reacting time and temperature can be varied accordingly. In oneembodiment the magnesium aluminosilicate comprises clay platelets withan average size of from about 5 nm to about 500 nm. In anotherembodiment the product comprises clay platelets with an average size offrom about 5 nm to about 50 nm.

The degree of stacking of the clay platelets is dependent on the ionicstrength of the second reaction mixture. A high ionic strength will givemuch-stacked structures, while a low ionic strength will lead tostructures exhibiting little stacking. The ionic strength of the secondreaction mixture can be adjusted by increasing or decreasing theconcentration of reactants (silicon, aluminum, and magnesium components)and altering the pH. For example, a dilute solution with a pH about 8will have a lower ionic strength than a solution with a highconcentration of reactants and a pH higher than 8. In one embodiment,the clay platelets have a degree of stacking of between 1 to about 5, inanother embodiment the clay platelets have a degree of stacking ofbetween about 1 to about 3. The lower limit is constituted by unstackedclay platelets, which have a “degree of stacking” of 1. The twoparameters—the size of the clay platelets and the degree of stacking—canbe estimated by means of transmission electron microscopy (TEM) andpowder x-ray diffraction respectively. In an embodiment, the powderx-ray diffraction of the magnesium aluminosilicate clay of the inventionhas only broad peaks. Broad peaks are indicative of a low degree ofstacking.

The individual clay platelets are composed of sheets of octahedrallycoordinated metal ions interlinked by means of oxygen ions and sheets oftetrahedrally coordinated metal ions interlinked by oxygen ions. Theapical oxygen atoms of the tetrahedral sheets help form the base of theoctahedral sheets, thus connecting the sheets to one another. A regularassemblage of sheets (for example tetrahedral-octahedral ortetrahedral-octahedral-tetrahedral) is called a layer. If the sheetarrangement is tetrahedral-octahedral it is referred to as 1:1, if thesheet arrangement is tetrahedral-octahedral-tetrahedral it is referredto as 2:1. The product of the present invention can be described as a2:1 layered magnesium aluminosilicate.

The catalytic activity of the magnesium aluminosilicate clay stems inpart from the charge on the sheets. A neutral tetrahedral sheet requiresthat the tetrahedrally co-ordinated metal ion have a tetravalent charge.In general, the metal ion will be Si⁴⁺. To have a neutral octahedrallayer, the metal ions present in that layer will have to provide a totalcharge of 6+ for every three octahedral cavities. This can be achievedby filling two out of every three octahedral cavities with trivalentmetal ions, such as Al³⁺, or by filling all octahedral cavities of eachset of three with divalent metal ions, such as Mg²⁺. This gives twotypes of octahedral layers, trioctahedral layers, in which alloctahedral sites are filled and dioctahedral layers, which have twothirds of the octahedral sites filled. We believe that the product ofthe present invention comprises a 2:1 trioctahedral magnesiumaluminosilicate. For further description of clay classification see J.Theo Kloprogge, Sridhar Komarneni, and James E. Amonette, “Synthesis ofsmectite clay minerals; a critical review”Clays and Clay Minerals;October 1999; v. 47; no. 5; p. 529-554, herein incorporated byreference.

When lower valency cations are substituted or partially substituted forhigher valency cations in the clay platelet structure, the clay plateletis negatively charged. For instance, in the tetrahedral layer trivalentmetal ions, for example Al⁺³, may be substituted for a portion of thetetravalent metal ions such as Si⁺⁴. In the case of a clay with atrioctahedral layer structure, such as the product of the process of thepresent invention, such a substitution will give a saponite or avermiculite. The divalent Mg²⁺ metal ions in the octahedral layer can besubstituted or partially substituted by monovalent metal ions such asNa⁺, K⁺, or Li⁺.

In an embodiment of the magnesium aluminosilicate clay described above,at least 0.1 atomic %, as compared with the neutral clay mineral of thecations, can be replaced by cations of a lower valency. Preferably, atleast 1 atomic %, more preferably at least 5 atomic %, of the cations inthe clay platelets is replaced by cations of a lower valency. In theoctahedral layer, preferably not more than 50 atomic % of the metal ionsis replaced by ions of a lower valency as compared with the neutralsituation, more preferably not more than 30 atomic % is replaced. In thecase of the tetrahedral layer, preferably not more than 30 atomic % ofthe tetravalent metal ions present is replaced by metal ions of a lowervalency, more preferably not more than 15 atomic %. Isomorphoussubstitution may occur only in the octahedral layer, only in thetetrahedral layer, or in both layers. In this context the termisomorphous substitution also refers to the removal of cations withoutthe incorporation into the lattice of replacement cations, by whichvacancies are produced. It will be clear that this removal alsogenerates negative charges.

The neutral tetrahedral layer comprises Si⁴⁺ ions. At least a portion ofthe Si⁴⁺ ions can be substituted by trivalent ions to impart a negativecharge on the layer. The trivalent ions in the tetrahedral layerpreferably are aluminium (Al³⁺) ions, although other trivalent ions suchas chromium, cobalt (III), iron (III), manganese (III), titanium (III),gallium, vanadium, molybdenum, tungsten, indium, rhodium, and/orscandium can also be substituted. In an aspect of the invention, themagnesium aluminosilicate clay comprises at least 1 ppm Al³⁺ ions. Theneutral octahedral layer comprises divalent magnesium (Mg²⁺) ions,although other divalent ions such as nickel, cobalt (II), iron (II),manganese (II), copper (II) and/or beryllium can also be incorporatedinto the neutral octahedral layer. The divalent ions of the neutraloctahedral layer can be substituted by monovalent ions such as lithium(Li⁺) ions to impart a negative charge on the octahedral layer.

The negative charge generated by isomorphous substitution iscounterbalanced by the incorporation of cations, also known ascounter-ions, into the space between the clay platelets. Thesecounter-ions often are sodium or potassium. Generally, these cations areincorporated in the hydrated form, causing the clay to swell. For thisreason, clays with negatively charged clay platelets are also known asswelling clays. It is because of the negative charge caused byisomorphous substitution that clays can be advantageous for use incatalysis, since it gives them the potential to function as solid acids.However, to be able to function as solid acids, it is essential that theclay minerals comprise protons, since these are at least partiallyresponsible for the cracking ability of these compounds. Protons can beincorporated into the clay by replacing the non-hydrolyzablecounter-ions such as sodium or potassium with ammonium ions and thenheating the whole. This process will deammoniate the material, leaving aproton. Protons can also be introduced by replacing the counter-ionswith hydrolyzable metal ions such as Mn(II) and Ca(II).

Generally, a hydrolysable metal ion (M^(n+)) may hydrolyze according tothe following scheme, depending upon pH and concentration:M^(n+) +xOH⁻

M(OH)_(x) ^((n−x)+),  (1)M(OH)_(x) ^((n−x)+)+OH⁻

M(OH)_(x+1) ^((n−x+1)+),  (2)M(OH)_(x) ^((n−x)+)+H⁺

M(OH)_(x−1) ^((n−x+1)+)+H₂O.  (3)

With equation (3) yielding a proton.

While not being bound by any theory, we believe that the magnesiumaluminosilicate clays prepared by the synthesis process described aboveexhibit greater substitution of Al³⁺ in the tetrahedral layer thanmagnesium aluminosilicate clays prepared by initial formation of asilica-alumina gel. The high degree of substitution of Al³⁺ for Si⁴⁺results in a more active magnesium aluminosilicate clay after ionexchange and calcination due to higher acidity of the magnesiumaluminosilicate clay.

The magnesium aluminosilicate clay employed in the catalysts andprocesses of the invention can be characterized by surface area and porecharacteristics. The magnesium aluminosilicate clay of the presentinvention generally has a B.E.T. surface area in the range of 100 to1000 m²/g and preferably in the range of 400 to 900 m²/g. The magnesiumaluminosilicate clay has an average pore volume, determined by means ofB.E.T. nitrogen adsorption, in the range of 0.3 to 2.0 cc/g, preferablyin the range of at least 0.5 cc/g, and most preferably in the range ofat least 0.9 cc/g. The magnesium aluminosilicate clay has an averagepore size, determined by means of nitrogen adsorption/desorption in themesoporous range. In embodiments, the magnesium aluminosilicate clay ofthe present invention is mesoporous with an average pore size of about 2nm to about 50 nm.

In an embodiment, the magnesium aluminosilicate clay has a silicon toaluminum elemental mole ratio greater than 3. The ²⁹Si NMR of themagnesium aluminosilicate clay comprises peaks as given in Table 1.

Hydrocracking catalysts of the invention and employed in the process ofthe invention can be of widely varying composition, provided theycontain the magnesium aluminosilicate clay described above.Hydrocracking catalysts of the invention can comprise components in suchas metals, zeolites, other clays, molecular sieves, inorganic oxides,binders, diluents, and combinations thereof. The following examples ofcatalysts are not intended to limit in any way the scope of theinvention.

The magnesium aluminosilicate clay employed in the hydrocrackingcatalyst and process of the invention can act as a support for at leastone hydrogenation metal. As used herein “hydrogenation metal” refers toany metal or metal compound capable of lowering the energy of activationfor a hydrogenation reaction. As used herein “active metal” and“catalytically active metal” refers to any metal or metal compoundcapable of lowering the energy of activation for a hydrogenationreaction and is used interchangeably with “hydrogenation metal.”Examples of hydrogenation metals include, but are not limited to,nickel, platinum, palladium, ruthenium, tungsten, molybdenum, cobalt,iron, and rhodium. Generally, catalytically active metals are chosenfrom Group VIB and/or Group VIII of the periodic table. Other metalssuch as tin, germanium, lead, or compounds thereof, can be added aspromotors, particularly when the catalyst also contains nickel or acompound thereof. The promotor can be present in an amount of 0.1 to 30weight percent, preferably 0.2 to 15 weight percent, based on thecatalyst and calculated as metal.

The magnesium aluminosilicate clay employed in the invention can be inan acidic form or in a nonacidic form depending on the desiredapplication for the catalyst. When used in a hydrocracking catalyst, themagnesium aluminosilicate clay employed in the invention is preferablyin an acidic form. By “acidic form” it is meant that the magnesiumaluminosilicate clay is in a protonated or partially protonated form.This refers to the replacement of at least a portion of the non-acidiccations with protons to balance the negatively charged tetrahedraland/or negatively charged octahedral sheets.

When the magnesium aluminosilicate clay employed in the invention is inan acidic form, the magnesium aluminosilicate can crack the hydrocarbonfeedstock, contributing to the overall catalytic activity of thecatalyst composition.

In an embodiment, the hydrocracking catalyst of the invention comprisesthe magnesium aluminosilicate clay described above in combination withone or more zeolites, inorganic oxides, Group VIB metals, and/or GroupVIII metals.

Zeolites can be broadly described as crystalline microporous molecularsieves that possess three-dimensional frameworks composed of tetrahedralunits (TO_(4/2), T=Si, Al, or other tetrahedrally coordinated atom)linked through oxygen atoms. Zeolite X (FAU) and zeolite Beta areexamples of zeolites with large pores delimited by 12-membered ringswherein the pore aperture measures about 7.4 Å. The pores in zeolitesare often classified as small (8 T atoms), medium (10 T atoms), large(12 T atoms), or extra-large (≧14 T atoms) according to the number oftetrahedral atoms that surround the pore apertures. The classificationof intrazeolite channels as 1-, 2-, or 3-dimensional is set forth by R.M. Barrer in Zeolites, Science and Technology, edited by F. R.Rodrigues, L. D. Rollman and C. Naccache, NATO ASI Series, 1984 whichclassification is incorporated in its entirety by reference (seeparticularly page 75).

Other examples of large pore zeolites include, but are not limited to,zeolite Y, FAU, EMT, ITQ-21, ERT, and ITQ-33. These are documented athttp://topaz.ethz.ch/IZA-SC/StdAtlas.htm, and in Baerlocher, Meier, andOlson's “Atlas of Zeolite Framework Types”, Elsevier, 2001.

In one embodiment, the hydrocracking catalyst of the invention comprisesa large pore zeolite which has a Si:Al ratio in the range from about10:1 to about 100:1, preferably in the range from about 10:1 to about60:1. In a preferred embodiment the zeolite is a faujasite. The catalystcomposition employed in the process of the invention comprises activezeolite components ranging from about 1% to about 50% of the catalystcomposition.

Inorganic oxides such as silica, alumina, magnesia, titania, zirconia,and combinations thereof can be components of the catalyst employed inthe process of the invention. The inorganic oxide can contribute to theoverall catalytic activity of the catalyst composition throughcontribution of acid sites or the inorganic oxide can act as a diluentor binder. The inorganic oxide can function as filler material, actingas diluent of the cracking activity of the clay platelets, for example,thus making it possible to regulate the cracking activity of thecatalyst. The inorganic oxide can provide a matrix for one or morecatalytically active components, without providing catalytic activityitself, but improving the attrition resistance of the catalystcomposition. The amount of inorganic oxide to be added to thehydroprocessing catalysts of the invention generally depends on thedesired activity of the final catalyst composition and can range from 0%to about 95%. The inorganic oxide can provide increased surface area forthe catalytically active components of the catalyst composition. In oneembodiment, the inorganic oxide can be a mesoporous inorganic oxide withan average pore size from about 2 to 50 nm as measured by nitrogenadsorption/desorption. Preferably the average pore size of the inorganicoxide is between about 7.5 to 12 nm.

The hydrocracking catalyst of the invention can further comprise ahydrogenation component which is selected from a Group VIB metal, aGroup VIII metal, and combinations thereof. As will be evident to theskilled person, the word “component” in this context denotes themetallic form of the metal, its oxide form, or its sulphide form, or anyintermediate, depending on the situation. The hydrogenation metals areselected from the Periodic Table's Group VIB and Group VIII metals (CASPeriodic Table). The nature of the hydrogenation metal present in thecatalyst is dependent on the catalyst's envisaged application. If, forexample, the catalyst is to be used for hydrogenating aromatics inhydrocarbon feeds, the hydrogenation metal used preferably will be oneor more noble metals of Group VIII, preferably platinum, palladium, orcombinations thereof. In this case the Group VIII noble metal preferablyis present in an amount of 0.05-5 wt. %, more preferably in an amount of0.1 to 2 wt. %, and most preferably in an amount of 0.2 to 1 wt. %,calculated as metal. If the catalyst is to be used for removing sulphurand/or nitrogen, it will generally contain a Group VIB metal componentand/or a non-noble Group VIII metal component. In an embodiment, thehydrogenation metal is molybdenum, tungsten, nickel, cobalt, or amixture thereof. The Group VIB and/or non-noble Group VIII hydrogenationmetal preferably is present in an amount of 2 to 50 wt. %, morepreferably in an amount of 5 to 30 wt. %, most preferably in an amountof 5 to 25 wt. %, calculated as the metal oxide.

The magnesium aluminosilicate clay employed in the invention enables thehydrogenation metals, as described above, to be incorporated, at leastin part, into the magnesium aluminosilicate platelet structure. Forinstance, cobalt or nickel may be present in the octahedral layer. Inorder to be catalytically active, these metals must be removed from theclay platelet structure during catalyst use. This can be done, forexample, by means of reduction or sulphidation, for instance when thecatalyst is sulphided under reducing conditions prior to use.Alternatively, the hydrogenation metals can be incorporated into theinterlayer between the clay platelets through ion exchange. Regardlessof the incorporation site, the magnesium aluminosilicate clay helps todisperse the catalytically active metal.

Various methods of adding active metals to catalyst compositions areknown in the art. Briefly, methods of incorporating active metalsinclude ion exchange, homogeneous deposition precipitation, redoxchemistry, chemical vapor deposition, and impregnation. Preferably,impregnation is used to incorporate active metals into the catalystcomposition. Impregnation involves exposing the catalyst composition toa solution of the metal or metals to be incorporated followed byevaporation of the solvent. In an embodiment, chelating agents are usedduring metal impregnation. “Chelating agents” or “chelates” can bedescribed as a molecule containing one or more atoms capable of bondingto, or complexing with, a metal ion. The chelating agent acts as aligand to the Group VIB and/or Group VIII metal ions, often throughelectron pair donor atoms in the chelating agent. Chelated metal ionstend to be more soluble and chelating agents can improve the dispersionof metal ions throughout the catalyst composition. Chelates can bepolydentate, in that they can bond or complex to a metal ion through oneor more positions. For example a bidentate ligand forms two bonds with ametal ion, whereas a hexadentate ligand forms six bonds with a metalion. Examples of chelating agents include, but are not limited to,citrate, ethylene diamine tetraacetic acid (EDTA), ethylene glycoltetraacetic acid (EGTA), nitrilotriacetic acid (NTA), halides, nitrate,sulfate, acetate, salicylate, oxalate, and formate. Other examples ofchelates include, but are not limited to, carboxylic acid such asglycolic acid, lactic acid, tartaric acid, malic acid, maleic acid,citric acid, glyceric acid, gluconic acid, methoxy-acetic acid,ethoxy-acetic acid, malonic acid, succinic acid and glyoxylic acid andorganic sulfur compounds such as mercapto-acetic acid,1-mercapto-propionic acid, 2-mercaptopropionic acid,2,3-dimercapto-succinic acid, mercaptosuccinic acid, thio-acetic acid,thio-diglycolic acid, dithio-diglycolic acid, thio-salicylic acid,mercaptoethanol, β-thiodiglycol and thiourea. Other oxygen containingcompounds in addition to carboxylic acids can also be used as chelatingagents. Examples include, but are not limited to, ethylene glycol,propylene glycol, diethylene glycol, trimethyleneglycol,triethyleneglycol, ethyleneglycol monobutyl ether, diethylene glycolmonomethyl ether, diethylene glycol monomethylether, diethylene glycolmonopropyl ether, diethylene glycol monobutyl ether, glycerine,trimethylol ethane, and trimethyl propane. In an embodiment, nickelcitrate solutions are used to impregnate the catalyst composition. Otherexamples of metal ion-chelate complexes which can be used to impregnatea catalyst or catalyst composition with metals or metal ions includenickel-EDTA, nickel-acetate, nickel-formate, molybdenum-citrate,nickel-NTA, and molybdenum-NTA. For a review see A. Jos van Dillen, R.J. A. M. Terorde, D. J. Lensveld, J. W. Geus, and K. P. de Jong,

“Synthesis of supported catalysts by impregnantion and drying usingaqueous chelated metal complexes,” Journal of Catalysis, 2003, p.257-264, herein incorporated by reference in its entirety.

The Group VIB and/or Group VIII metals can be added to the magnesiumaluminosilicate clay prior to or after calcination of the magnesiumaluminosilicate clay. For example, the magnesium aluminosilicate claycan be (1) dried, impregnated with active metal(s), extruded, andcalcined, or (2) impregnated with active metal(s), extruded, andcalcined, (3) dried, extruded, dried or calcined, impregnated withactive metal(s), and calcined, or (4) dried, extruded, calcined, andimpregnated with active metals. The magnesium aluminosilicate clay canbe mixed with one or more components such as zeolites, crystallinecracking components, non-crystalline cracking components, catalyticallyinactive binders, diluents, and combinations thereof prior to or afterimpregnation with the GroupVIB and/or GroupVIII metals.

The order of addition of hydrocracking catalyst components to the finalhydrocracking catalyst can vary. Catalysts comprising the magnesiumaluminosilicate clay can be prepared in any way known in the art. Forinstance, the magnesium aluminosilicate clay can be extruded intoparticles, the particles calcined, and then the calcined particlesimpregnated with an impregnating solution containing salts of thehydrogenation metals to be introduced, optionally in combination withother components such as phosphoric acid, and/or complexing agents.Alternatively, the magnesium aluminosilicate can be mixed with othersupport materials such as amorphous alumina, silica alumina, and thelike which may have their own catalytic activity, whereupon this mixturecan be extruded and the resulting extrudates calcined. The calcinedextrudates can then be impregnated as described above. It is alsopossible to add certain hydrogenation metal components to the catalystcomposition prior to extrusion, more particularly, it is proposed to mixthe magnesium aluminosilicate employed in the process of the inventionand any other support materials with molybdenum oxide, after which theresulting mixture is extruded and calcined.

If the catalyst contains non-noble Group VIII metals and/or Group VIBmetals as hydrogenation metals, it is preferably sulfided prior to use.This involves converting the metal components in the catalyst to theirsulfided form. The sulfiding can be done by means of processes known tothe skilled person, for example, by contacting the catalyst in thereactor at rising temperature with hydrogen and a sulfurous feed, orwith a mixture of hydrogen and hydrogen sulfide. Ex situ presulfiding isalso possible. Sulfurizing conditions include a temperature range of200°-400° C. preferably 250°-300° C. and a pressure variable betweenatmospheric and high. The sulfurizing agent can be elemental sulfur,mercaptans, thiophene, or mixtures of hydrogen and hydrogen sulfide.

After sulfurization, the catalyst is ready to be used in either aconventional fixed bed reactor or an ebullating bed reactor.

If the catalyst contains a Group VIII noble metal, there is no need forsulfiding as a rule, and a reducing step, for example, with hydrogen,will suffice.

Generally, the magnesium aluminosilicate clay employed in the inventioncan comprise from about 1% to about 99.9% of the hydrocracking catalyst.For example, catalysts are envisaged containing 1-99.9 wt. % of themagnesium aluminosilicate clay, 0-25 wt. % of a zeolite component,0.1-35 wt. % of a hydrogenation metal component, 0-97.9 wt. % ofmesoporous alumina, and the balance inorganic oxide matrix material.Suitable inorganic oxide matrix materials are, for example, alumina,silica, titania, zirconia, and combinations thereof. In one embodimentthe inorganic oxide matrix material is alumina. In one embodiment, thehydrocracking catalyst of the present invention comprises 0.1 wt. %platinum, palladium, or combinations thereof and 99.9% magnesiumaluminosilicate clay of the present invention. In another embodiment,the hydrocracking catalyst comprises (1) 20 to 30 wt. % Group VIB metal,non-noble Group VIII metal, or combinations thereof, (2) 0.5 to 60 wt. %large pore zeolite such as zeolite Y, and (3) 10 to 79.5 wt % magnesiumaluminosilicate clay, wherein the magnesium aluminosilicate clay issynthesized according to the process steps outlined above.

In an embodiment, the catalyst comprises 5-20 wt. %, preferably 8-16 wt.%, of a Group VIB metal, calculated as the oxide. Generally, if lessthan 5 wt. % is used, the activity of the catalyst is insufficient. Onthe other hand, if more than 20 wt. %, is used, the catalyticperformance is not improved further.

In another embodiment, the catalyst comprises 0.5-6 wt. %, preferably1-5 wt. %, of Group VIII metal, calculated as oxide. If the amount isless than 0.5 wt. %, the activity of the catalyst will be too low. Ifmore than 6 wt. % is present, the catalyst performance will not beimproved further.

Optionally, a promoter such as a phosphorus, boron, silicon, orcombinations thereof can be added as in known in the art. For example,it will be obvious to the skilled person that phosphorus can beincorporated into the catalyst in a suitable manner by contacting thecatalyst during any one of its formative stages with an appropriatequantity of a phosphorus-containing compound, e.g., phosphoric acid. Forinstance, the catalyst can be impregnated with an impregnating solutioncomprising phosphorus in addition to any other components. If thecatalyst according to the invention contains phosphorus, this compoundis preferably present in an amount of 0.5-10 wt. %, calculated as P₂O₅,based on the weight of the catalyst composition.

The catalysts described above can be in the form of particles of manydifferent shapes. The suitable shapes include spheres, cylinders, rings,and symmetric or asymmetric polylobes, for instance tri- andquadrulobes. The particles usually have a diameter in the range of 0.5to 10 mm, and their length likewise is in the range of 0.5 to 10 mm.

The process of the invention can employ a wide variety ofhydrocarbonaceous feedstocks. Hydrocarbonaceous feedstocks containcarbon compounds and can be from many different sources, such as virginpetroleum fractions, recycle petroleum fractions, shale oil, liquefiedcoal, tar sand oil, synthetic paraffins from NAO, recycled plasticfeedstocks, biologically derived feedstocks such as plant oils, plantwaxes, animal fats, animal oils, and combinations thereof. Other feedsinclude synthetic feeds, such as those derived from a Fischer Tropschprocess, including an oxygenate-containing Fischer Tropsch processboiling below about 371° C. (700° F.). Examples of feedstocks include,but are not limited to, petroleum distillates, solvent-deasphaltedpetroleum residua, shale oils coal tar distillates, and hydrocarbonfeedstocks derived from plant, animal, and/or algal sources. Thefeedstocks can boil above 200° F. The feedstocks can contain substantialamounts of materials boiling in the range 350 to 950° F., and evensubstantial amounts of materials boiling in the range 400 to 900° F.Other suitable feedstocks include those heavy distillates normallydefined as heavy straight-run gas oils and heavy cracked cycle oils, aswell as conventional FCC feed and portions thereof. In general, the feedcan be any carbon containing feedstock susceptible to hydroprocessingcatalytic reactions. Depending on the type of processing thehydrocarbonaceous feed is to undergo, the feed can contain metal or befree of metals, it can also have high or low nitrogen or sulfurimpurities.

The hydrocarbonaceous feedstocks which can be effectively treated by thecatalyst include those which contain vanadium, nickel, arsenic, iron, orcombinations thereof. The vanadium, nickel, arsenic, and/or ironcontents of the feedstocks can exceed 1000 ppm. The feedstocks cancomprise asphaltenes in amounts greater than 5 wt. %. The feedstocks cancomprise asphaltenes in amounts greater than 8 wt. %. In someembodiments, the feedstocks can comprise asphaltenes in amounts greaterthan 25 wt. %. In embodiments, the feedstock comprises a vanadiumcontent of greater than 50 ppm vanadium. In another embodiment thefeedstock comprises a vanadium content of greater than 100 ppm vanadium.The sulfur content of the feedstocks to be processed can vary. Sulfurcontents of 1%, 2% or greater are possible. Sulfur content of thefeedstocks can be lower than 1%. Nitrogen content of the feedstocks canrange from 0 ppm to greater than 1000 ppm.

Cracked stocks can be obtained from thermal or catalytic cracking ofvarious stocks, including those obtained from petroleum, gilsonite,shale and coal tar. The feedstocks can be subjected to a hydrofiningtreatment, a hydrogenation treatment, a hydrocracking treatment, orcombinations thereof, prior to contact with the catalyst of theinvention. Organic nitrogen content of the feedstock is generally lessthan 1000 parts per million (ppm), preferably 0.5 to 500 parts permillion, and more preferably, 0.5 to 100 parts per million. Whencontacting the catalyst of this invention, it is preferable to maintainthe organic sulfur content of the feedstock in a range of from about 0to 3 weight percent, preferably from 0 to 1 weight percent.

The hydrocracking of hydrocarbonaceous feeds can take place in anyconvenient mode, for example, in fluidized bed, moving bed, or fixed bedreactors depending on the types of process desired. The formulation ofthe catalyst particles will vary depending on the process and method ofoperation.

In an embodiment, the present invention is directed to a hydrocrackingprocess comprising contacting a hydrocarbon feedstock underhydrocracking conditions with a catalyst comprising a magnesiumaluminosilicate clay wherein said magnesium aluminosilicate clay issynthesized by a process comprising the following steps:

-   -   a) combining (1) a silicon component, (2) an aluminum component,        and (3) a magnesium component, under aqueous conditions at a        first reaction temperature and at ambient pressure, to form a        first reaction mixture, wherein the pH of said first reaction        mixture is acidic;    -   b) adding an alkali base to the first reaction mixture to form a        second reaction mixture having a pH greater than the pH of the        first reaction mixture; and    -   c) reacting the second reaction mixture at a second reaction        temperature and for a time sufficient to form a product        comprising a magnesium aluminosilicate clay.

In an embodiment, the invention is directed to hydrocracking processescomprising the step of contacting a hydrocarbonaceous feedstock with acatalyst composition comprising a magnesium aluminosilicate clay whereinthe magnesium aluminosilicate clay has a silicon to aluminum elementalmole ratio greater than 3 and wherein the ²⁹Si NMR of the magnesiumaluminosilicate clay comprises peaks as given in Table 1.

In another aspect, the invention is directed to a hydrocracking catalystcomprising a magnesium aluminosilicate clay wherein the magnesiumaluminosilicate clay has a silicon to aluminum elemental mole ratiogreater than 3 and wherein the ²⁹Si NMR of the magnesium aluminosilicateclay comprises peaks as given in Table 1.

Any suitable reaction time (contact time) between the hydrocrackingcatalyst, hydrogen and the hydrocarbonaceous feedstock can be utilized.In general, the contact time will range from about 0.1 hours to about 10hours. Preferably, the reaction time will range from about 0.4 to about4 hours. Thus the flow rate of the hydrocarbon-containing feed stream ina continuous operation should be such that the time required for thepassage of the mixture through the reactor (residence time) will be inthe range of from about 0.1 to about 10 hours, and preferably be in therange of from about 0.4 to about 4 hours. This generally requires aliquid hourly space velocity (LHSV) in the range of about 0.10 to about10 cc of oil feed per cc of catalyst per hour, preferably from about 0.2to about 2.5 cc/cc/hr.

According to one embodiment, the hydrocarbon feed is placed in contactwith the hydrocracking catalyst in the presence of hydrogen, usually ina fixed bed reactor. The conditions of the hydrocracking process mayvary according to the nature of the feed, the intended quality of theproducts, and the particular facilities of each refinery. Thetemperature is usually greater than 200° C., and is often comprisedbetween 250° C. and 480° C. Pressure is usually greater than 0.5 bar andoften greater than 10 bar. The H₂/hydrocarbon ratio is usually greaterthan 100 and usually between 150 and 15,000 scfb. Liquid hourly spacevelocity (LHSV) is generally between 0.01 and 20 feed volumes percatalyst volume per hour. The hydrocracking process according to thisparticular embodiment is preferably performed at temperatures from 250°C. to 320° C.

Other hydroprocessing catalysts and reactions are also envisagedemploying the magnesium aluminosilicate described above. Hydrocrackingin combination with hydrodemetallization is a hydroprocessing reactionenvisaged for catalysts comprising the magnesium aluminosilicatedescribed herein. Table 2 gives general process conditions for catalystscomprising the magnesium aluminosilicate described above.

TABLE 2 Process Temp., ° C. Pressure LHSV Hydrocracking 175-485 0.5-350bar 0.1-30 Dewaxing 200-475 15-3000 psig, 0.1-20 (250-450) (200-3000psig) (0.2-10) Aromatics 400-600 atm.-10 bar 0.1-15 formation (480-550)Cat. Cracking 127-885 subatm.-¹ 0.5-50 (atm.-5 atm.) Oligomerization 232-649² 0.1-50 atm.^(2,3)  0.2-50²   10-232⁴ —  0.05-20⁵    (27-204)⁴—  (0.1-10)⁵ Isomerization  93-538 50-1000 psig,   1-10 (204-315)  (1-4)¹Several hundred atmospheres ²Gas phase reaction ³Hydrocarbon partialpressure ⁴Liquid phase reaction ⁵WHSV

Catalyst compositions comprising the magnesium aluminosilicate claydescribed above, wherein the magnesium aluminosilicate clay ispredominantly in the protonated form, can be used to dewaxhydrocarbonaceous feeds by cracking and/or isomerizing straight chainparaffins. Typically, the viscosity index of the dewaxed product isimproved (compared to the waxy feed) when the waxy feed is contactedwith said catalyst compositions under isomerization dewaxing conditions.

The catalytic dewaxing conditions are dependent in large measure on thefeed used and upon the desired pour point. Hydrogen is typically presentin the reaction zone during the catalytic dewaxing process. The hydrogento feed ratio is typically between about 500 and about 30,000 SCF/bbl(standard cubic feet per barrel) (0.089 to 5.34 SCM/liter) (standardcubic meters/liter), for example about 1000 to about 20,000 SCF/bbl(0.178 to 3.56 SCM/liter). Generally, hydrogen will be separated fromthe product and recycled to the reaction zone. Typical feedstocksinclude light gas oil, heavy gas oils and reduced crudes boiling aboveabout 350° F. (177° C.).

A typical dewaxing process is the catalytic dewaxing of a hydrocarbonoil feedstock boiling above about 350° F. (177° C.) and containingstraight chain and slightly branched chain hydrocarbons by contactingthe hydrocarbon oil feedstock in the presence of added hydrogen gas at ahydrogen pressure of about 15-3000 psi (0.103-20.7 Mpa) with a catalystcomprising the magnesium aluminosilicate described above and at leastone Group VIII and/or Group VIB metal. Optionally, a promoter such as aphosphorus, boron, silicon, or combinations thereof can be added as inknown in the art. The catalyst may be run in such a mode to increaseisomerization dewaxing at the expense of cracking reactions.

Catalyst compositions comprising the magnesium aluminosilicate claysemployed in the invention, wherein the magnesium aluminosilicate claysare predominantly in the protonated form, can be used to make lube oil.For example, a C₂₀₊ lube oil may be made by isomerizing a C₂₀₊ olefinfeed over a catalyst comprising the magnesium aluminosilicate.Preferably, the magnesium aluminosilicate is in the protonated form.Preferably the catalyst further comprises at least one Group VIII metal.Alternatively, the lubricating oil may be made by hydrocracking in ahydrocracking zone a hydrocarbonaceous feedstock to obtain an effluentcomprising a hydrocracked oil, and catalytically dewaxing the effluentat a temperature of at least about 400° F. (204° C.) and at a pressureof from about 15 psig to about 3000 psig (0.103-20.7 Mpa gauge) in thepresence of added hydrogen gas with a catalyst comprising the magnesiumaluminosilicate employed in the process of the invention.

The magnesium aluminosilicate clay of the invention can be used incatalysts for catalytic cracking. Preferably the magnesiumaluminosilicate is in the protonated form. Hydrocarbonaceous feedstockscan be catalytically cracked in the absence of hydrogen using acatalytic cracking catalyst.

Catalytic cracking catalysts can further comprise any aluminosilicateheretofore employed as a component in cracking catalysts. Typically,these are large pore, crystalline aluminosilicates. Examples of thesetraditional cracking catalysts are disclosed in U.S. Pat. No. 4,910,006and U.S. Pat. No. 5,316,753. When a traditional cracking catalyst (TC)component is employed, the relative weight ratio of the TC to themagnesium aluminosilicate employed in the process of the invention isgenerally between about 1:10 and about 500:1, desirably between about1:10 and about 200:1, for example between about 1:2 and about 50:1 orbetween about 1:1 and about 20:1.

The cracking catalysts are typically employed with an inorganic oxidematrix component. See the aforementioned U.S. Pat. No. 4,910,006 andU.S. Pat. No. 5,316,753 for examples of such matrix components.

During hydrotreatment, oxygen, sulfur and nitrogen present in thehydrocarbonaceous feed is reduced to low levels. Aromatics and olefins,if present in the feed, may also have their double bonds saturated. Insome cases, the hydrotreating catalyst and hydrotreating conditions areselected to minimize cracking reactions, which can reduce the yield ofthe most desulfided product (typically useful as a fuel).

Hydrotreating conditions typically include a reaction temperaturebetween 400-900° F. (204-482° C.), for example 650-850° F. (343-454°C.); a pressure between 500 and 5000 psig (3.5-34.6 Mpa), for example1000 to 3000 psig (7.0-20.8 MPa); a feed rate (LHSV) of 0.5 hr⁻¹ to 20hr⁻¹ (v/v); and overall hydrogen consumption 300 to 2000 scf per barrelof liquid hydrocarbon feed (53.4-356 m³ H₂/m³ feed). Hydrotreatingcatalysts can comprise the magnesium aluminosilicate described above.

While not being bound by any theory, we believe that catalystcompositions comprising the magnesium aluminosilicate clay of theinvention as described above are particularly suited for hydroprocessingreactions such as the hydrocracking of high molecular weighthydrocarbons because of the large surface area, pore structure, and highdensity of acid sites of the magnesium aluminosilicate clays employed inthe process of the present invention. Relatively large size organicmolecules, such as high molecular weight hydrocarbons (hydrocarbonshaving greater than 20 carbon atoms) and aromatic compounds, canpenetrate the mesopores of the magnesium aluminosilicate clays employedin the process of the present invention or react with acid sites on thesurface of the magnesium aluminosilicate clays. The magnesiumaluminosilicate clay employed in the process of the invention, with itsextensive surface area, helps disperse active Group VIB and/or GroupVIII metals, providing more discreet sites for hydrogenation reactionsto occur. Furthermore, the magnesium aluminosilicate clay comprising thecatalysts of the invention and employed in the process of the inventionexhibit higher activity than magnesium aluminosilicate clays synthesizedby other methods, likely due to increased incorporation of Al³⁺ into thetetrahedral sheets, leading to higher acid site density and a moreactive catalyst composition.

EXAMPLES Example 1 (Comparative)

A magnesium aluminosilicate with an elemental composition Mg 5.7[Si 6.4Al 1.6]O 20 (OH)₄ with a Si/Al=4 was prepared as follows. Water glass(sodium silicate) (27 wt. % SiO₂) was mixed with aluminum nitrate atroom temperature to form a silica-alumina gel. The mixture was thenfiltered and added to a solution of magnesium nitrate and the pHadjusted with NaOH to about 8.8. The reaction was allowed to proceed for40 hours at 90° C. after which time the reaction mixture was filteredand washed. The filtrate was a magnesium aluminosilicate clay.

Example 2

A magnesium aluminosilicate clay with an elemental composition Mg5.4[Si6.6 Al 1.4]O 20 (OH)₄ with a Si/Al=4.7 was prepared as follows. Waterglass (27 wt. % SiO₂) was mixed with aluminum nitrate at roomtemperature and the pH adjusted to about 1 with nitric acid. A solutionof magnesium nitrate was added to form a first reaction mixture. The pHof the first reaction mixture was acidic. The pH of the first reactionmixture was then adjusted to about 8.4 with the addition of NaOH to forma second reaction mixture. The reaction was allowed to proceed for 1hour at 50° C. after which time the second reaction mixture was filteredand washed. The filtrate was the magnesium aluminosilicate clay of theinvention.

Example 3 (Comparative)

The magnesium aluminosilicate clay of Example 1 was added to a 0.1 Msolution of ammonium nitrate to exchange the sodium cations for ammoniumcations. The ammonium substituted magnesium aluminosilicate clay wascollected by filtration and washed with water. The ammonium substitutedmagnesium aluminosilicate clay was then calcined at 450° C. degrees for12 hours to convert the magnesium aluminosilicate clay to the protonatedform.

Example 4

The magnesium aluminosilicate clay of Example 2 was added to a 0.1 Msolution of ammonium nitrate to exchange the sodium cations for ammoniumcations. The ammonium substituted magnesium aluminosilicate clay wascollected by filtration and washed with water. The ammonium substitutedmagnesium aluminosilicate clay was then calcined at 450° C. degrees for12 hours to convert the magnesium aluminosilicate clay to the protonatedform.

Example 5 (Comparative)

Amorphous silica-alumina (71.3 wt. %) was mixed with faujasite (5.7 wt.%), and mesoporous alumina (23 wt. %) under aqueous conditions in thepresence of dilute nitric acid to form an extrudable mixture. Thematerial was extruded, dried at 250° F. for one hour, and then calcinedat 1100° F. for one hour. The calcined extrudate was then mixed with asolution of nickel and tungsten salts. The mixture was allowed to soakfor 2 hr., then dried at 270° F. for 0.5 hours. After drying, thematerial was calcined at 950° F. for 1 hour. The metal content of thefinal catalyst was approximately 5 wt. % NiO and 25 wt. % WO₃.

Example 6 (Comparative)

The magnesium aluminosilicate clay of Comparative Example 3 (44.8 wt. %)was mixed with faujasite (5.5 wt. %), boehmite (16.2 wt. %), andmesoporous alumina (33.4 wt. %) under aqueous conditions in the presenceof dilute nitric acid to form a slurry. Water soluble methylcellulosederived polymer (Methocel Dow Corp.) was added to achieve an extrudablemixture (less than 1 wt. % methocel added). The mixture was extruded,dried at 250° F., and calcined at 1100° F. for one hour to form acalcined extrudate. The calcined extrudate was then mixed with asolution of nickel and tungsten salts in the presence of citrate. Themixture was allowed to soak for 1 hr., then dried at 212° F. for 2hours. The metal content of the final catalyst was 5 wt. % NiO and 25wt. % WO₃.

Example 7

The magnesium aluminosilicate of the invention, Example 4, (44.8 wt. %)was mixed with faujasite (5.5 wt. %), boehmite (16.2 wt. %), andmesoporous alumina (33.4 wt. %) under aqueous conditions in the presenceof dilute nitric acid to form a slurry. Water soluble methylcellulosederived polymer (Methocel Dow Corp.) was added to achieve an extrudablemixture (less than 1 wt. % methocel added). The mixture was extruded,dried at 250° F., and calcined at 1100° F. for one hour to form acalcined extrudate. The calcined extrudate was then mixed with asolution of nickel and tungsten salts in the presence of citrate. Themixture was allowed to soak for 1 hr., then dried at 212° F. for 2hours. The metal content of the final catalyst was approximately 5 wt. %NiO and 25 wt. % WO₃.

Example 8

The catalysts of Example 6 (Comparative), Example 7 (Comparative), andExample 8 (invention) were sulfided and compared for hydrocrackingactivity on a feedstock with the characteristics given in Table 3.

TABLE 3 Feedstock Nitrogen (ppm) 1152 Sulfur (wt. %) 2.70 wax (wt. %)11.1 VI 72 vis 100° C. 9.645 API 19.8 IBP¹ 638  5% 694 10% 734 20% 77030% 805 40% 836 50% 866 60% 894 70% 923 80% 956 90% 991 95% 1013 end1055 ¹Initial Boiling Point

Hydrocracking results are given in Table 4 for a 60% conversion of thefeedstock. Reaction conditions included a pressure of 2300 psig, a molarratio of hydrogen to hydrocarbon of 5000 scfb and a feed rate of 0.75hr⁻¹ LHSV.

TABLE 4 Example 5 Example 6 Example 7 (Comparative) (Comparative)(invention) T req 60% (° F.) 743 745 745 C4- 2.0 2.1 2.1 C5-180° F. 3.53.1 2.5 180-250° F. 5.3 5.1 4.7 250-550° F. 34.1 34.0 34.0 550-700° F.16.6 17.4 18.5 700-800° F. 14.9 15.3 15.2 800-900° F. 13.5 12.7 12.8900° F.+ 9.5 9.6 9.6 W viscosity 5.244 5.040 4.940 100° C. (cSt) Waxy VI700° F.+ 144 146 150 DWO (dewaxed oil) 5.112 5.067 4.922 viscosity 100°C. (cSt) DWO (dewaxed oil) VI 132 132 132 (Viscosity Index) 700° F.+

Table 4 demonstrates that the catalyst comprising the magnesiumaluminosilicate of the invention has improved yield of middle distillatein fuels hydrocracking than a catalyst comprising a magnesiumaluminosilicate synthesized by prior art methods or a conventionalcatalyst of amorphous silica alumina, zeolite, and alumina binder. Thetemperature required for 60% conversion is similar for all threecatalysts. However, the yield in the middle distillate range (550-700°F.) is highest for the hydrocracking catalyst of the invention.

The invention claimed is:
 1. A hydrocracking catalyst useful in preparing middle distillate, comprising: a magnesium aluminosilicate clay having a silicon to aluminum elemental mole ratio greater than 3 and wherein the ²⁹Si NMR of the magnesium aluminosilicate clay comprises the following peaks: Chemical Peaks shift (ppm)¹ P1 −79 P2 −82 P3 −85 P4 −88 P5  −93, ¹+/−3 ppm

and a zeolite; with the magnesium aluminosilicate clay comprising from about 1 wt. % to about 95 wt. % of the hydrocracking catalyst; with the magnesium aluminosilicate clay in the protonated form; wherein the magnesium aluminosilicate clay is synthesized according to a method comprising the following steps: a) combining (1) a silicon component, (2) an aluminum component, and (3) a magnesium component, under aqueous conditions at a first reaction temperature and at ambient pressure, to form a first reaction mixture, wherein the pH of said first reaction mixture is in the range of from 0 to about 5; b) adding an alkali base to the first reaction mixture to form a second reaction mixture wherein the pH of the second reaction mixture is greater than 7.5, and c) reacting the second reaction mixture at a second reaction temperature and for a time sufficient to form a product comprising a magnesium aluminosilicate clay, and with the hydrocracking catalyst comprising a Group VIB metal, Group VIII metal, or a combination thereof.
 2. The hydrocracking catalyst of claim 1, wherein the magnesium aluminosilicate clay comprises from about 5 wt. % to about 50 wt. % of the hydrocracking catalyst.
 3. The hydrocracking catalyst of claim 1, wherein the magnesium aluminosilicate clay is calcined.
 4. The hydrocracking catalyst of claim 1, further comprising an inorganic oxide.
 5. The hydrocracking catalyst of claim 4, wherein the inorganic oxide is selected from the group consisting of silica, alumina, magnesia, titania, zirconia, and combinations thereof.
 6. The hydrocracking catalyst of claim 1, wherein the zeolite is a large pore zeolite.
 7. The hydrocracking catalyst of claim 6, wherein the large pore zeolite is selected from the group consisting of faujasite, zeolite Y, zeolite beta, EMT, ITQ-21, ERT, ITQ-33, and combinations thereof.
 8. The hydrocracking catalyst of claim 1, wherein the hydrocracking catalyst is sulfided.
 9. The hydrocracking catalyst of claim 1, wherein the Group VIB metal is chromium, molybdenum, tungsten, or combinations thereof.
 10. The hydrocracking catalyst of claim 1, wherein the Group VIII metal is nickel, cobalt, iron, ruthenium, rhodium, iridium, platinum, palladium, or combinations thereof.
 11. The hydrocracking catalyst of claim 1, further comprising a promoter selected from the group consisting of boron, silicon, phosphorus, tin, germanium, lead, and combinations thereof. 